Method of processing hydrocarbon oils



Feb. 6. 1934. Q c BLACK 1,945,508-

METHOD OF PROCESSING-HYDROCARBON' OILS Filed Jan. 21, 1930 Illlllll INVENTOR 7 BY JOHN C, 54/704 ATTORNE Patented Feb. 6, 1934 1,945,508 METHOD or rnoca l na mznnocsnnon John C. Black, Beverly Hills, Calif. Application January 21, 1930. Serial No. 422,405

Claims.

.This invention relates to an improved method of cracking hydrocarbon oils, such as mineral oils, petroleum oils, shale oils or distillates, of the same, to produce an improved motor fuel or gas- 5 oline stock suitable as a fuel for internal combustion engines with a high compression ratio, or as a solvent for the extraction of oils from vegetable products and the like.

This application is a continuation in part of my pending application Ser. No. 376,228 filed July 5, 1929 for Process of producing an improved motor fuel and solvent oil.

Briefly stated, my invention comprises separately separating by vaporization, pressureregulation andvfractionation, a lower boiling naphtha fraction and a higher boiling naphtha fraction from cracked hydrocarbon oils products, con- I densing and collecting the lower boiling naphtha fraction, subjecting the separated higher boiling naphtha fraction while in a vapor state to a thermo molecular decomposition action at a temperature sufliciently high to convert the major portion of the same into carbocyclic hydrocarbons, then separating by fractionation and condensation that portion of the converted naphtha fraction which has boiling points up to approximately 450 degrees F.,- or any other desired end point and then commingling the same with the first mentioned lower boiling naphtha fraction, or with any other gasoline or naphtha stock, to produce gasoline stock having any desired range of boiling points.

It is usually necessary to purify the naphtha stocks with sulphuric acid and other purifying agents to obtain a water white gasoline with a reduced sulphur content and which will be sweet to the doctor test. This purifying operation may be carried out by any of the purifying methods known in the art, either before or after blendins.

In case a solvent naphtha for the extraction of oils from vegetable products, or a cleaners naphtha stock is desired, the converted naphtha stock containing a high percentage of carbocyclic hydrocarbons having boiling points up to apD .oximately 450 degrees F. is preferably employed after a purification and fractionation operation.

The gasoline or naphtha stock made by this process may also be chemically treated and purified by any of the well-known vapor phase processes.

An object of the invention is to produce gasoline stock or motor fuel for use in internal combustlon 'engines with a high compression ratio.

Another object of the invention is to produce used as a by valve 3. Pipe 2, controlled by valve 3, cona motor fuel suitable for use in internal combustion engines with a high compression ratio without requiring the use of anti-knock compounds.

Another object of the invention is to produce a solvent naphtha stock w ch may be employed to extract oils from vegetable products or may be cleaning fluid.

Another object of the invention is to provide 'a continuous process for converting by a thermo molecular decomposition operation, the higher boiling fraction of a-gasoline or naphtha stock, into a non-detonating motor fuel containing a high percentage of carbocyclic hydrocarbons, such as benzol, toluol, xylol, etc. or as a blending stock for gasolines having detonating properties to render the latter non-detonating.

Another object of the invention is to increase the non-detonating properties of cracked gasoline or naphtha stocks by a continuous operation while the same is in the process of manufacture. 76

Various other objects and advantages of the present invention will be apparent from the description of the preferred form or example of the process embodying the invention.

For this purpose, reference is made to the accompanying drawing in which there is illustrated a form of apparatus in which the invention may be performed.

The drawing represents a diagrammatic view of the apparatus in which the parts are in vertical section.

In the drawing 1 is a tank containing the oil to be processed or cracked. The oil is introduced into the tank 1 through pipe 2' controlled nects tank 1 to the inlet side of pump 4. Pipe 5 connects the discharge side of pump 4 to heating coil 7 stationed in furnace 6. Furnace 6 is provided with a burner 84. Pipe 39 connects pipe 5 to pipe 42. Pipe 8 controlled by pressure regulating and discharge valve 9 connects heating coil 7 to vaporizing tower 10. Pipe 40, controlled by valve 41, connects pipe 39 to pipe 8. Pipe 8 is provided with pressure gauge 82 and vaporizing tower 10 is provided with pressure gauge 82'. vaporizing tower 10 is provided with trays 11. Pipe 81, controlled by valve 80, connects the bottom of vaporizing tower 10 to a stor age not shown. Pipe 20, controlled by pressure regulating and discharge valve 21,- connects vaporizing tower 10 to'vaporizing tower 22, which is provided with trays 11'. .Va'porizing tower 22 is also provided with pressure gauge 83. Pipe 23, controlled by pressure regulating and discharge valve 24, connects the top of vaporizing tower 22 to heating coil 26, situated in the furnace 25. Furnace 25 is provided with a burner 85. Pipe 55, controlled by valves 54 and 56, connects the bottom of vaporizing tower 22 to fraotionating tower 57 just below the separator plate 58.

Pipe 27 is provided with a pressure gauge 83. Pipe 27, controlled by pressure regulating and discharge valve 28, connects heating coil 26 to fractionating tower 29 just below the separator plate 58'. Pipe 42, controlled by valve 43, connects pipe 39 to pipe 27. Fractionating tower 29 is provided with'bubble caps 30. Pipe 31 connects fractionating tower 29 at the top, to condenser coil 32, situated in condenser box 31'. Pipe 33 connects condenser coil 32 to look box 34. Pipe 98' is connected to look box 34 at the top and leads to an absorber not shown.

Pipe 12, controlled by pressure regulating and discharge valve 13, connects vaporizing tower 10 at the top to condenser coil 15, which is stationed in condenser box 31'. Pipe 16 connects condenser coil 15 to look box 17. Pipe 18 connects look box 17 to tank 19. Pipe 98 is connected to look box 17 which leads to an absorber not shown. Pipe 99, controlled by valve 100, connects tank 19 to a storage not shown. Pipe 102, controlled by valve 102, connects tank 19 to tank 103. Pipe 101, controlled by valve 101, connects tank 36 to pipe 102. Pipe 104, controlled by valve 104', connects tank 103 to a storage not shown.

Pipe 35 connects look box 34 to tank 36. Pipe 37, controlled by valve 38, connects tank 36 to a storage not shown. Pipe 44 connects fractionating tower 29 to cooling coil 46 stationed in cooling box 45. Pipe 47 connects cooling coil 46 to' tank 48. Pipe 92, controlled by valve 91, con-- nects distillate tank 48 to a storage not shown.

Pipe 50, controlled by valve 49, connects fractionating tower 29 at the bottom to cooling coil 51, situated in the cooling box 45. Pipe 52 connects cooling coil 51 to tank 53. Pipe 94, controlled by valve 93, connects tank 53 to a storage not shown.

Fractionating tower 57 is provided with checker brick work 59. Pipe 73, controlled by valve 72, connects fractionating tower 57 at the bottom, to cooling coil stationed in cooling box 74. Pipe 76 connects coil 75 to tank 77. Pipe 96, controlled by valve 95, connects tank 77 to a storage not shown.

Pipe 66 connects fractionating tower 57 just above the separator plate 58 to cooling coil 68 stationed in cooling box 67. Pipe 69 connects cooling coil 68 to distillate tank 70. Pipe 71 connects tank 70 to the inlet sideiof pump 63. Pipe 65 controlled by valve 64 connects the discharge side of pump 63 to a storage not shown.

Pipe 61,- controlled by valve 62 connects the discharge side of pump 63 to spray pipe 60. Pipe 29' connects fractionating tower 57 to cooling coil 86 situated in cooling box 97. Cooling coil 86 is connected to look box 87. Pipe 88 connects look box 87 to tank 89. Pipe 90, controlled by valve 90, connects tank 89 to a storage not shown.

The preferred process as carried out in the apparatus just described, is as follows:

Tank 1 is filledwith the hydrocarbon oil to be processed or cracked, by opening valve 3' inthe.

pipe 2'. Pipe 2' leads to a source of hydrocarbon oil supply not shown, such as a petroleum oil residuum or gas oil stock. The petroleum oil stock contained in tank 1 is caused to pass in a regulated stream flow through pipe 2 into the inletside of pump 4, by opening valve 3. Pump 4 continuously discharges the petroleum oil stock through pipe 5 and into heating coil 7, stationed in the upper section of furnace 6. The furnace 6 is provided with a burner 84 which is regulated to continuously supply sufiicient heat to heating coil 7 so that the petroleum oil stock passing in stream flow through'the heating coil 7 will be heated to, and maintained at, a cracking temperature of approximately 800 to 900 degrees F. for a period of time suflicient to crack the oil to the desired degree. The oil passing through the heating coil 7 is maintained under a pressure sufiicient to prevent any substantial vaporization, preferably at a terminal pressure of approximately 1000 pounds gauge, although higher or lower pressures may be employed, depending upon the stock to be cracked, the temperature employed and the time of passage of the oil through the coil 7. The products of the cracking reaction pass from heating coil 7 into pipe 8 wherein a cool bypassed stream of uncracked oil may be introduced into the cracked oil stream from pipe 40, the flow being controlled by valve 41, in quantities sufiicient to lower the temperature of the cracked oil stream below an active cracking temperature. Pipe 40 is connected to pipe 39 and pipe 39 is connected to pipe 5. Likewise oil from pipe 39 may be introduced into pipe 27 through pipe 42 and valve 43 for the same reason as above described, for the injection of oil into pipe 8 through pipe 40 and valve 41.

The oil stream passing through pipe 8 is discharged through pressure regulating and discharge valve 9 into the evaporator 10 where by means of pressure regulating valve 13 in vapor outlet line 12 and pressure regulating valve 21 in line 20, a pressure may be maintained in evaporator 10 sufficient to permit the lower boiling fractions to vaporize and pass out through valve 13 into the condenser 15 which is operated at approximately atmospheric pressure; that is, a pressure is maintained in evaporator 10 which will permit the low boiling fractions to vaporize and at the same time the higher boiling fractions will be held in liquid phase and discharged together withthe uncracked high boiling oils through valve 21 and pipe 20 into evaporator 22.

The pressure maintained on evaporator 10 by pressure regulating valves 13 and 21 will depend upon the vapor tension of the low boiling fraction which it is desired to remove, which in turn depends upon the characteristics of the hydrocarbons under treatment, upon its temperature and upon the amount to be vaporized.

I have found that from 40 to 60 per cent of the naphtha stock will form a desirable fraction to be removed as above described, leaving the balance of the naphtha stock to be removed in the next step of the process by substantially similar means to those described above. This second vaporization of the higher boiling fractions of the naphtha stock will occur in evaporator 22 and the pressure maintained on said evaporator will be sufiicient to permit this fraction to vaporize and at the same time to hold in liquid phase the uncracked high boiling hydrocarbons. The vaporized fraction is discharged through pressure regulating and. discharge valve 24 in pipe 23, and is conducted into the heater 25 through the secondary cracking coil 26 and under a pressure of 50 to 100 lbs. or more maintained by pressure regulating and discharge valve 28. In coil 26 the hydrocarbon vapor is subjected to a temperature of 900 to 1200 degrees F. and decomposition occurs with the production of carbocyclic hydrocarbons. The latter constitute the hydrocarbons desired to render the finished gasoline non-detonating. From the coil 26 the cracked vapors pass through pipe 2'1 and are discharged through valve 28 into the fractionating column 29 where the gasoline fraction is separated from the higher boiling fractions produced in the cracking reaction and from those fractions that were unconverted, or not desired in the final product. The latter fraction passes out of column 29 through pipe 31 and into condenser 32 thence by pipe 33 and look-box 34 and pipe 35 into the storage tank 36, said tank being fitted with a draw-off pipe 37 and valve 38.

The residue or unvaporized portion accumulated in the lower portion of evaporator 22 is continuously drawn off through pipe '55 and dis-, charge valve 54 and is discharged through valve 56 into the evaporator 57'where a further vaporization takes place with the separation of a heavy high boiling residue collected below the separator plate 58 and a lower boiling fraction condensed in the'checker brick work 59 and collected upon the plate 58 and discharged through pipe 66 into the cooling coil 68, pipe 69 and into tank'70. There is also a low boiling fraction, together with steam, which is conducted through pipe 29 into the condensing coil 86, look box 87, pipe 88 and into tank 89.

The oil collected in tank 70, tank 48 and tank 89 may be run to tank 1 and subjected to recracking. The two gasoline fractions in tanks 19 and 36 may be blended if desired, by opening valves 101' and 102' in pipes 101 and 102, which permits these two gasoline stocks to mix in pipe 102 and then pass into tank 103. From tank 103 the blended gasoline stock may be conducted to other storage tanks not shown through pipe 104 by operationof valve 104. The residues collected intanks 53 and 77 may be used as fuel oil or for other purposes. Thus it will be seenthat by proper manipulation of the pressures in the evaporators, the several fractions may be separated from the original stream of oil with but a single heating, the several fractions so produced entering into the various phases of the process, as described.

The pressures maintained throughout the system are indicated by the pressure gauges 82, 82', 83 and 83'; v

As anyone skilled in the art to which this process pertains will readily understand the various uses of the individual parts, in describing the above operation the function of each numbered part of the apparatus was not recited.

While the process herein described is well adapted for carrying out the objects of the present invention, various modifications and changes may be made without departing from the spirit of the invention, such as thez addition of any of the well-known heatexchange systems to preheat the oil to be processed or to add heat to the oil or oil vapors during the processing operation, and the invention includesall such modifications and changes as come within the scope of the appended claims.

What I claim is: I

1.- A process of producing gasoline stock with improved anti-detonating characteristics, comprising, cracking a petroleum oil under superatmospheric pressure, at temperatures of approximately 800-900 degrees F., to produce cracked petroleum oil products containing gasoline stock;

passing the hot cracked petroleum oil products 7 into a primary zone of lower pressure and vaporizing, separating, condensing and collecting only a lower boiling portion of the gasoline stock; passing the hot residual cracked petroleum oil products from the said primary zone of lower pressure into a secondary zone of still lower pressure, and vaporizing and separating the remaining, higher boiling portion of the gasoline stock from the residual oil products; passing only the separated vaporizedhigher boiling portion of the gasoline stock through a heated zone at tem-' peratures of approximately 900-1200 degrees F., injecting a cool hydrocarbon oil, as the cracked product leaves the heated zone,-in quantities sufficient to lower the temperature of the vaporized cracked products below an active cracking temperature and to crack the injected oil, and separating reformed gasoline stock, containing a high percentage of hydrocarbons of the carbocyclic series possessing anti-detonating characteristics, from the products of the secondary cracking operation.

2. A process of producing gasoline stock possessing anti-detonating characteristics, comprising, passing a petroleum oil-through a primary 1 cracking zone under superatmospheric pressure; at temperatures of approximately 800-900 degrees F., and cracking the petroleum oil to produce cracked petroleum oil products containing gasoline stock; injecting a cool hydrocarbon oil, as the 195 cracked products leave the primary cracking zone, in quantities sufiicient to lower the temperature of the cracked petroleum oil products below an active cracking temperature and to crack the injected oil; passing the hot cracked petroleum oil products from the primary cracking zone into a primary zone of lower pressure, and vaporizing, separating, condensing and collecting only a lower boiling portion of the gasoline stock; passing the hot residual cracked petroleum oil products into a secondary zone of still lower pressure, and vaporizing and separating the remaining, higher boiling portion of the gasoline stock from the residual cracked petroleum oil products; passing only the-separated va- 1 0 porized higher boiling gasoline stock througha secondary cracking zone at temperatures of approximately 900-1200 degrees 1 R, injecting a cool hydrocarbon oil, as the cracked product leaves the secondary cracking zone, in quantities sumcient to lower the temperature of the vaporized cracked products below an active cracking temperature and to crack the injected oil, and separating reformed gasoline stock, containing a high percentage of hydrocarbons of the carbo- 1 cyclic series possessing anti-detonating charac, teristics, from the products of the secondarycracking operation. 3. A process of producing gasoline stock possessing anti-detonatlngcharacteristics, comprising, cracking petroleum oil undersuperatmospheric pressure and producing cracked petroleum oil products containing gasoline stock; passing the hot cracked petroleum oil products into a primary vaporizing zone of lower pressure, and

vaporizing, separating, condensing and collecting only a lower boiling portion of the gasoline stock; passing the hot residual cracked petroleum: oil products from the primary vaporizing zone of lower pressure into a secondary vaporizing zone of still lower pressure, and vaporizing andseparating the remaining, higher boiling portion of the gasolinestock from residual oil products; passing only the separated vaporized higher boiling portion of the gasoline stock through a heating zone at temperatures of 900 F. or above, injecting a cooler hydrocarbon oil, as the cracked products leave the heating zone, in quantities sufiicient to lower the temperature of the vaporized cracked products below an active cracking temperature, and separating reformed gasoline stock, containing a high percentage of hydrocarbons of the carbocyclic series possessing antidetonating characteristics, from products of the secondary cracking operation.

4. A process of producing motor fuel possessing anti-detonating' characteristics, comprising, passing petroleum oil through a primary cracking zone under superatmospheric pressure, and cracking the petroleum oil to produce'cracked petroleum oil products containing gasoline stock; injecting a cooler hydrocarbon oil, as the cracked products leave the primary cracking zone, in quantities sufficient to lower the temperature of the cracked petroleum oil products below an active cracking temperature; passing the hot cracked petroleum oil products from the primary cracking coil into a primary vaporizing zone of lower pressure, and vaporizing, separating, condensing and collecting only a lower boiling portion of the gasoline stock; passing the hot residual cracked petroleum oil products from the primary vaporizing zone into a secondary vaporizing zone of still lower pressure, and vaporizing and separating the remaining, higher boiling portion of the gasoline stock from the residual cracked petroleum oil products; passing only the separated vaporized higher boiling gasoline stock through a secondary cracking zone at temperatures of approximately 9001200 F., injecting a cooler hydrocarbon oil as the cracked products leave the secondary cracking zone, in quantities sufiicient to lower the temperature of the vaporized cracked products below an active cracking temperature, separating reformed gasoline stock, containing a high percentage of hydrocarbons of the carbomary cracking zone at temperatures ranging from r 800 to 900 F., under superatmospheric pressure, and producing cracked petroleum oil products containing gasoline stock; passing the hot cracked petroleum oil productsfrom the primary cracking zone into a primary vaporizing zone of lower pressure; subjecting the hot cracked products in the primary vaporizing zone to fractional vaporization and separating therefrom only a lower boiling portion of the gasoline stock; condensing and collecting the separated lower boiling portion of the gasoline stock; passing the hot residual cracked petroleum oil products from the primary vaporizing zone into a secondary vaporizing zone of still lower pressure, and fractionating, ing and separating the remaining, higher'boiling portion of the gasoline stock from the residual cracked petroleum oil products; passing only the separated vaporized higher boiling gasoline stock through a secondary cracking zone at temperatures ranging from 900 to 1200 F., separating reformed gasoline stock, containing a high percentage of hydrocarbons of the carbocyclic series, from products of the secondary cracking operation, and commingling said separated reformed gasoline stock with the lower boiling portion of the gasoline stock primarily separated to produce a motor fuel with improved anti-detonating characteristics.

JOHN 0. BLACK.

vaporiz- 

